JP2602865B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a specific silicon atom and capable of crosslinking by forming a cycloxane bond. The present invention relates to a curable composition containing a hydrogenated polyconjugated diene polymer having 1.3 to 5 molecular terminals per molecule and a silanol condensation catalyst.

[Problems to be solved by conventional technologies and inventions]

Known oxyalkylene polymers having a reactive silicon group at the molecular terminal are low in viscosity, excellent in workability, cured by moisture even at room temperature, and have a low elastic modulus and high elongation, which is a rubber-like cured product. It is used in large quantities because of its interesting property that it can be obtained. However, the polymer has a problem that heat resistance, water resistance, weather resistance and the like are insufficient.

Further, the present inventors have also studied a polyisobutylene-based polymer having a reactive silicon group at the molecular terminal,
It has been found that a cured product from this polymer is excellent in heat resistance, water resistance, weather resistance, moisture barrier properties and the like. However, the polymer is 1,4-bis (α-chloroisopropyl)
Manufactured by a special method such as the inifer method (US Pat. No. 4,276,394) in which benzene is used as an initiator and chain transfer agent, and BCl ₃ is used as a catalyst to carry out cationic polymerization of isobutylene at a low temperature of −number + ° C. It must be produced from an isobutylene-based polymer having a (CH ₃ ) ₂ Cl group, which is not easy to produce.

[Means for solving the problem]

The present invention solves the problems of the conventional curable polymer as described above, is rapidly cured by moisture in the air at room temperature, elongation properties, heat resistance, water resistance, adhesion, weather resistance,
Dielectric constant, giving excellent rubber-like cured product such as electrical properties such as insulating properties, and was made for the purpose of obtaining a composition containing a curable polymer that is easy to produce,
(A) A polymer having a number-average molecular weight of 500 to 30,000 and mainly comprising a hydrogenated conjugated diene unit, having a general formula (1): (Wherein R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or (R ′) ₃ SiO— (R ′ 1 of carbon number 1-20
Is a trivalent hydrocarbon group, and three R's may be the same or different), and when two or more R ¹ or R ² are present, They may be the same or different, X is a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group,
An aminooxy group, a mercapto group or an alkenyloxy group, and when two or more Xs are present, they may be the same or different; a is 0, 1, 2 or 3, b is 0 , 1 or 2, where a + mb ≧ 1 and m B need not be the same, m is 0 or 1 to
A hydrogenated polyconjugated diene-based polymer having 1.3 to 5 groups represented by the following formula (hereinafter also referred to as a reactive silicon group) per molecule and (B) a silanol condensation catalyst. It relates to a curable composition.

[Examples] The hydrogenated polyconjugated diene polymer used in the present invention (hereinafter, referred to as
Abbreviated as hydrogenated polydiene polymer) has a number average molecular weight of 500
It is a polymer mainly composed of hydrogenated conjugated diene units (hereinafter abbreviated as hydrogenated diene units) of up to 30,000, preferably 1,000 to 15,000.

When mainly composed of hydrogenated diene units, 50% or more, preferably 75% or more, of a polymer is a conjugated diene compound (hereinafter abbreviated as a diene compound) (for example, butadiene, isoprene, chloroprene, etc. (Preferably butadiene) means a unit derived from hydrogenation. The other units constituting the polymer have a copolymerizability with the diene compound used if necessary when polymerizing the diene compound. If necessary, a CH ₂ ＣC (R ³ ) -group (where R ³ is a hydrogen atom or a carbon atom) is introduced to introduce a reactive silicon group to the terminal of the unit having a hydrogenated polydiene polymer. And a group derived from a group such as a monovalent organic group having the number of 1 to 20, and a residue of a compound used for introducing a reactive silicon group into a terminal.

When the number-average molecular weight of the polymer used in the present invention is 500 terminals, the ratio of hydrogenated diene units in the polymer may not be the main component, and good weatherability caused by the hydrogenated polydiene-based polymer, Characteristics such as heat resistance, water resistance, and special electric properties cannot be sufficiently obtained. On the other hand, if the average molecular weight exceeds 30,000, there is no problem as to the properties of the polymer, but it is not preferable because the viscosity becomes too high to make it difficult to handle during production or use. In particular, a liquid substance having a number average molecular weight of about 1,000 to 15,000 to a substance having fluidity is preferable from the viewpoint of handleability and the like.

The polymer used in the present invention has 1.3 to 5, preferably 1.5 to 3, general formula (I) per molecule: (Wherein R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or (R ′) ₃ SiO— (R ′ 1 of carbon number 1-20
Is a trivalent hydrocarbon group, and three R's may be the same or different), and when two or more R ¹ or R ² are present, They may be the same or different, X is a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group,
An aminooxy group, a mercapto group or an alkenyloxy group, and when two or more Xs are present, they may be the same or different; a is 0, 1, 2 or 3, b is 0 , 1 or 2, where a + mb ≧ 1 and m B need not be the same, m is 0 or 1 to
A reactive silicon group is present at the terminal of the molecule.

If the number of reactive silicon groups contained in the molecule is less than 1.3, the curability becomes insufficient and a cured product exhibiting good rubber elasticity behavior cannot be obtained.

Among the specific examples of X in the general formula (I), an alkoxy group, an acyloxy group, an aminooxy group, an alkenyloxy group, and the like are preferable, and a methoxy group, an ethoxy group, etc. In particular, when the hydrolyzable group is a group that is difficult to handle such as a halogen atom or a hydrogen atom, it is preferable to use the compound after converting it to an alkoxy group.

X in the general formula (I) represents 1 to 3
, But (a + mb) is 1 to
A range of 5 is preferred. When X is bonded to two or more reactive silicon groups, they may be the same or different.

The number of silicon atoms forming the reactive silicon group may be one, or two or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably up to 20. Especially the formula: (Wherein, R ² , X and a are the same as those described above) are preferred because they are easily available.

Specific examples of R ² in the general formula (1) include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and the like. And a triorganosiloxy group represented by (R ') ₃ SiO-, wherein R' is a methyl group, a phenyl group or the like. Of these, a methyl group is particularly preferred.

The reactive silicon group exists at the terminal of the molecular chain of the water-fueled polydiene-based polymer, and in this case, the effective network chain amount of the hydrogenated polydiene-based polymer component contained in the finally formed cured product is large. Therefore, it is preferable in that a rubbery cured product having high strength and high elongation can be easily obtained. These hydrogenated polydiene polymers having a reactive silicon group may be used alone or in combination of two or more.

The polymer constituting the skeleton of the hydrogenated polydiene-based polymer having a reactive silicon group used in the present invention is a conjugated diene-based compound such as butadiene, isoprene, and chloroprene (hereinafter, referred to as conjugated diene-based compound).
A diene compound) may be obtained by polymerizing one or more kinds, followed by hydrogenation, but can be easily obtained by introducing a functional group into a terminal. A hydrogenated polybutadiene-based polymer is preferred from the viewpoint that the molecular weight can be easily controlled and the number of terminal functional groups can be increased.

In the hydrogenated polydiene-based polymer, all of the monomer units may be formed from hydrogenated diene units, and the diene-based compound and a monomer unit having copolymerizability may be contained in the hydrogenated polydiene-based polymer. Preferably 50% (% by weight, hereinafter the same) or less, more preferably 25% or less, particularly preferably 10%
It may be contained in the following range.

Such monomer components include, for example, those having 2 to 2 carbon atoms.
12, preferably olefins having 2 to 6 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, acrylic compounds and the like. Specific examples of such a copolymer component include, for example, ethylene,
Propylene, 1-butene, isobutylene, 2-butene,
2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-
Methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethyl Silane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane,
Allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxy Examples include silane and acrylonitrile.

The use of vinylsilanes or allylsilanes as monomers having copolymerizability with the diene compound increases the silicon content, increases the number of groups that can act as silane coupling agents, and increases the adhesiveness of the resulting polymer. Is improved.

Next, a method for producing a hydrogenated polydiene polymer having a reactive silicon group will be described.

Among the hydrogenated polydiene-based polymers having a reactive silicon group, hydrogenated polydiene-based polymers having a reactive silicon group at the molecular chain terminal are, for example, hydroxyl-terminated, carboxyl-terminated and other terminal functionalized hydrogenated polydiene-based polymers. It can be produced using a polymer.

For example, a hydrogenated polybutadiene-based polymer will be described as an example. First, the hydroxyl groups of the terminal hydroxy-hydrogenated polybutadiene-based polymer are converted to oxymetal groups such as -ONa and -OK. (In this example, a hydroxyl group-terminated hydrogenated polybutadiene-based polymer is described, but a similar reaction can proceed with carboxyl group-terminated hydrogenated polybutadiene.)
Thereafter, the general formula (2): CH ₂ ＣC (R ⁴ ) —R ⁵ —Y (2) (wherein, Y is a halogen atom such as a chlorine atom or an iodine atom, and R ⁴ is a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. 20 monovalent organic groups,
R ⁵ is -R ^6- , (R ⁶ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and specific preferred examples thereof include an alkylene group, a cycloalkylene group, an arylene group, and an aralkylene group.)
In valent organic group, -CH ₂ -, (R ″ is preferably a divalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms), thereby reacting an organic halogen compound represented by the following formula (1) to obtain a hydrogenated polybutadiene-based polymer having a terminal olefin group ( Hereinafter, this is also referred to as a hydrogenated polybutadiene polymer having terminal olefins).

The terminal hydroxyl groups of the terminal hydroxy hydrogenated polybutadiene polymer as a method for the oxy metal group, Na, alkali metal K such as; such metal hydride NaH; NaOCH ₃ in such a metal alkoxide; sodium hydroxide, such as potassium hydroxide caustic And the like.

In the above method, a terminal olefin hydrogenated polybutadiene-based polymer having substantially the same molecular weight as the terminal hydroxy-hydrogenated polybutadiene-based polymer used as a starting material can be obtained, but if a polymer having a higher molecular weight is desired, a general method is used. Before reacting the organic halogen compound of the formula (2), a polyvalent organic halogen compound containing two or more halogen atoms in one molecule, such as methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether, etc. When the reaction is carried out with the organic halogen compound represented by the general formula (2), the molecular weight can be increased.
A hydrogenated polybutadiene polymer having a higher molecular weight and having an olefin group at the terminal can be obtained.

Specific examples of the organic halogen compound represented by the general formula (2) include, for example, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) Ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene,
Examples include, but are not limited to, allyloxy (chloromethyl) benzene. Of these, allyl chloride is preferred because it is inexpensive and easily reacts.

A reactive silicon group is introduced into the terminal olefin hydrogenated polybutadiene polymer. For example, a hydrosilane compound in which a hydrogen atom is bonded to a group represented by the general formula (1),
Preferably the general formula: (Wherein R ² , X and a are the same as those described above), and a group VIII transition metal compound such as a platinum compound as a catalyst is used as a catalyst of the general formula (3): CH ₂ ＣC (R ⁴ ) —R ⁵ O _c (3) (wherein R ⁴ and R ⁵ are the same as above, and c is 0 or 1). The polymer used in the present invention is produced by an addition reaction to the unsaturated group.

Specific examples of the hydrosilane compound in which a hydrogen atom is bonded to the group represented by the general formula (1) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, trimethoxysilane, and the like. Alkoxysilanes such as ethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoxime) methylsilane, bis (cyclohexylke) Examples include, but are not limited to, ketoxime silanes such as (toximate) methyl silane.
Of these, halogenated silanes and alkoxysilanes are particularly preferred.

As another method for introducing a functional group into the terminal, a hydroxyl group-terminated polymer is reacted with a polyisocyanate compound such as toluene diisocyanate to obtain an isocyanate group-terminated polymer, and then the isocyanate is represented by the general formula (4): (Where W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary), R ⁷ is a divalent organic group having 1 to 20 carbon atoms, R ² , X and a are the same as those described above), and a group of a silicon compound W represented by the following formula is reacted. In the olefin group of the hydrogenated polydiene-based polymer having an olefin group represented by the general formula (3), W is a mercapto group A method of adding a mercapto group of a silicon compound represented by the general formula (4), and a method of adding a general formula (5) to a hydroxyl group or a carboxyl group of a hydroxyl group-terminated polymer. (Wherein, R ² , R ⁷ , X and a are the same as described above), and the like, but are not limited thereto.

In the above method, after reacting them, some or all of the X groups may be further converted to other hydrolyzable groups or hydroxyl groups.

In the general formula (2) or (3), R ⁴ is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and is preferably a hydrogen atom or a hydrocarbon group. It is preferably a hydrogen atom. In addition,
While R ⁷ is a divalent organic group having 1 to 20 carbon atoms, -R ⁸ -, -
R ⁸ OR ⁸ −, (R ⁸ is a divalent hydrocarbon group having 1 to 10 carbon atoms), and particularly preferably a methylene group.

A hydrogenated polydiene polymer having a reactive silicon group in the molecular chain is obtained by adding a vinyl compound having a functional group such as a hydroxyl group or an allylsilane to a monomer mainly composed of a diene compound and copolymerizing the monomer. Thereafter, it is produced by a method such as hydrogenation, and then introduction of a reactive silicon group using the above functional group such as a hydroxyl group.

Furthermore, during the polymerization at the time of producing the hydrogenated polydiene polymer having a reactive silicon group at the molecular chain end, a vinyl monomer having a functional group such as a hydroxyl group in addition to the diene compound as a main component was copolymerized. Thereafter, a functional group is first introduced into the terminal, and then a reactive silicon group is introduced using the functional group, whereby a hydrogenated polydiene polymer having a reactive silicon group at the terminal and in the molecular chain is produced.

The polymer used in the present invention can be easily produced by an ordinary method, and is cured by moisture in the air at room temperature, and has heat resistance, water resistance, weather resistance, adhesiveness, as well as elongation characteristics and strength. A rubber-like elastic body having good properties and electrical properties is provided. Therefore, the polymer used in the present invention can be suitably used as a sealing agent, an adhesive, a pressure-sensitive adhesive, a paint, a waterproofing agent, a molding material, a cast rubber material, and the like. In order to cure the hydrogenated polydiene polymer used in the present invention, a silanol condensation catalyst is used. Examples of such a condensation catalyst include titanates such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylate salts such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; dibutyltin oxide and phthalate Reaction products with acid esters; dibutyltin diacetylacetonate; organic aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate, titanium tetraacetylacetonate Chelating compounds of the formula: lead octylate; butylamine, monoethanolamine, triethylenetetramine, guar Jin, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7
Amine compounds such as (DBU) or salts thereof such as carboxylic acids; and other known silanol catalysts such as acidic catalysts and basic catalysts.

When using the composition of the present invention, various additives may be added as necessary. Examples of such additives include:
For example, a physical property modifier such as a silane compound, various fillers, a plasticizer, water, an antioxidant, an ultraviolet absorber, a lubricant, a pigment, a foaming agent, an adhesion-imparting agent and the like can be mentioned.

Examples of physical property modifiers for controlling physical properties such as strength and elongation of the cured product include (CH ₃ ) ₃ SiOH,
(CH ₃ CH ₂ ) ₃ SiOH, (CH ₃ CH ₂ CH ₂ ) SiOH ₃ , _{(CH 3) 2 Si (OCH} 3) 2, (CH 3 CH 2) 2 Si (OCH 3) 2, (CH 3) 2 Si (OCH 2 CH 3) 2, (CH 3 CH 2) 2 Si (OCH ₂ CH ₃ )
₂ , _{(CH 3) 2 Si (OCH} 2 CH 2 OCH 3) 2, (CH 3 CH 2) 2 Si (OCH 2 CH 2 OCH 3) 2, (CH 3) (CH 3 CH 2) Si (OCH 3) 2 , (CH ₃ ) ₃ SiN (CH ₃ ) ₂ , And a silicon compound containing at least one silanol group. However, the present invention is not limited thereto. Note that R in the formula is a hydrogen atom or carbon number 1
~ 20 hydrocarbon groups.

There are roughly three methods for adding these silicon compounds.

One is a method of simply adding the compound to the hydrogenated polydiene-based polymer. Depending on the properties of the compound,
If necessary, they may be uniformly dispersed and dissolved by heating and stirring. In this case, it is not necessary to make it completely transparent in a uniform state. Even if it is in an opaque state, the purpose can be sufficiently achieved if it is dispersed. If necessary, a dispersibility improver such as a surfactant may be used in combination.

A second method is to add and mix a predetermined amount of the compound when finally using the product. For example, when used as a two-component sealing agent, the compound may be used as a third component in addition to the base and the curing agent.

In the third method, the compound is reacted with the hydrogenated polydiene-based polymer in advance, and a tin-based catalyst, a titanate-based catalyst, an acid, or a basic catalyst may be used if necessary. In the case of a compound that produces a compound containing a silanol group by moisture, the required amount of water is also added, and the object is achieved by heating and devolatilization under reduced pressure.

Specific examples of the catalyst that can be used in this case include titanates such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylate salts such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; Lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine,
Triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine,
Guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N
Amine compounds such as -methylmorpholine and 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) or salts thereof with carboxylic acids; low molecular weight obtained from excess polyamine and polybasic acid Polyamide resin; reaction product of excess polyamine and epoxy compound; silane coupling agent having amino group, for example, silanol condensation of γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, etc. Catalysts and the like. These catalysts may be used alone or in combination of two or more.

As fillers, for example, wood flour, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, clay,
Examples include fumed silica, precipitated silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, aluminum fine powder, flint powder, and zinc powder. These fillers may be used alone or in combination of two or more.

As a plasticizer, polybutene, hydrogenated polybutene,
hydrocarbon compounds such as α-methylstyrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylenetriphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyldiphenyl and partially hydrogenated terphenyl; paraffin chloride; dibutyl phthalate Phthalic acid esters such as diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate and butylphthalylbutyl glycolate; non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; diethylene glycol benzoate; Esters of polyalkylene glycols such as triethylene glycol dibenzoate; phosphate esters such as tricrene diphosphate and tributyl phosphate; It is below. These may be used alone or in combination of two or more. These plasticizers may be used in place of the solvent for the purpose of adjusting the reaction temperature and adjusting the viscosity of the reaction system when introducing the reactive silicon group into the hydrogenated polydiene polymer.

Specific examples of the adhesion-imparting agent include various silane coupling agents such as an epoxy resin, a phenol resin, an aminosilane compound, and an epoxysilane compound, alkyl titanates, and aromatic polyisocyanates. By using two or more kinds, it is possible to improve the adhesion to various kinds of adherends.

 Next, the composition of the present invention will be described based on examples.

Production Example 1 Hydrogenated polybutadiene at both ends (Polytail H
A, manufactured by Mitsubishi Chemical Corporation, hydroxyl value 51, iodine value 4.7)
176 g of a MeOH solution of NaOCH ₃ (concentration: 28%) was added to 800 g, and the oxymetallation reaction was performed for about 5 hours while devolatilizing at 130 ° C. Thereafter, 99.1 g of 3-chloro-2-methyl-1-propene was added, and the mixture was reacted at 90 ° C. for 3 hours and purified.

The obtained liquid polymer was analyzed by an NMR method and a GPC method, and as a result, it was a polymer having an average molecular weight of 3500 in which an isopropenyl group was introduced into 76% of all terminals.

40 g of the polymer having an average molecular weight of 3500 and toluene
The mixture was weighed in a one-necked flask and degassed under reduced pressure at 90 ° C. for 2 hours. Then, under a nitrogen atmosphere, a solution prepared by dissolving 4.6 g of methyldichlorosilane in dry heptane and a chloroplatinic acid catalyst solution 13.5 μm
After the addition of _{(H 2 PtCl 6 · 6H 2} O in 0.2 mol / isopropyl alcohol solution) at room temperature and reacted for 8 hours at 85 ° C..

When the amount of the remaining isopropenyl group in the reaction solution was quantified by IR spectroscopy, it was found that almost no residue remained.

Next, 8.7 ml of methyl orthoformate and 3.2 ml of methanol were added and reacted at 70 ° C. for 3 hours.

At this point, the pH of the reaction system reached about 7, indicating neutralization.
After distilling off the volatile components under reduced pressure, 50 ml of hexane was added to the residual components.
And stir well to remove any insoluble matter,
Hexane was distilled off from the liquid.

The amount of reactive silicon groups in the obtained polymer was determined by NMR. Almost 100% of the isopropenyl groups at the molecular terminals were (CH ₃ O ₂ ) Si (CH ₃ ) CH ₂ CH (CH ₃ ) CH ₂ It was found to be an O-group.

Examples 1 and 2 100 parts (parts by weight, hereinafter the same) of the polymer obtained in Production Example 1 were 50 parts of polybutene (polybutene OH manufactured by Idemitsu Petrochemical Co., Ltd.) as a plasticizer and calcium carbonate as a filler.
100 parts, 3 parts of tin octylate and 0.75 part of laurylamine as a curing catalyst (silanol condensation catalyst), 1 part of dilaurylthiodipropionate as an antioxidant (Example 1) or 2 (2'-hydroxy-3 ', One part of 5'-di-t-butylphenyl) benzotriazole (Example 2) was added, and the mixture was kneaded well with a three-roll mill to prepare a curable composition. The obtained composition is in the form of a sheet (plate) with a thickness of about 3 mm.
4 days at room temperature and 4 days at 50 ° C
Cured in air for days.

The cured product of Example 1 was heated in an oven at 130 ° C. to evaluate the heat resistance of the cured product according to the time required for the surface to begin to melt. However, the surface of the cured product did not change after 300 days. The sheet-like cured product itself did not have any resinification or softening.

The weather resistance of the cured product of Example 2 was measured using a sunshine carbon arc weather meter (120 minute cycle, spray 18
Min), and an attempt was made to evaluate the surface by the time at which the surface began to melt, but no change was observed on the surface of the cured product even after 5000 hours. The sheet-like cured product itself did not have any resinification or softening.

〔The invention's effect〕

The composition of the present invention can be easily produced by a usual method, and is cured at room temperature by moisture in the air, and has heat resistance, water resistance, weather resistance, adhesiveness, as well as elongation characteristics and strength. And a rubber-like elastic body having good electrical properties.

Claims (3)

(57) [Claims] 1. A polymer having a number average molecular weight of 500 to 30,000 and mainly composed of hydrogenated conjugated diene units, which is represented by the following general formula (1): (Wherein R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or (R ′) ₃ SiO— (R ′ 1 of carbon number 1-20
Is a trivalent hydrocarbon group, and three R's may be the same or different), and when two or more R ¹ or R ² are present, They may be the same or different, X is a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group,
An aminooxy group, a mercapto group or an alkenyloxy group, and when two or more Xs are present, they may be the same or different; a is 0, 1, 2 or 3, b is 0 , 1 or 2, where a + mb ≧ 1 and m B need not be the same, m is 0 or 1 to
A hydrogenated polyconjugated diene-based polymer having 1.3 to 5 groups represented by the following formula:
A curable composition containing a silanol condensation catalyst. 2. The composition according to claim 1, wherein X in the general formula (1) is an alkoxy group. 3. The composition according to claim 1, wherein said hydrogenated polyconjugated diene-based polymer is a hydrogenated polybutadiene-based polymer.